US8580224B2 - Method for increasing the sulfuric acid concentration of a sulfuric acid solution - Google Patents

Method for increasing the sulfuric acid concentration of a sulfuric acid solution Download PDF

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Publication number
US8580224B2
US8580224B2 US13/884,887 US201113884887A US8580224B2 US 8580224 B2 US8580224 B2 US 8580224B2 US 201113884887 A US201113884887 A US 201113884887A US 8580224 B2 US8580224 B2 US 8580224B2
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sulfuric acid
acid solution
concentrated
hydrogen peroxide
concentration
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US20130236389A1 (en
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Hendrikus Johannes Koehorst
Teunis Leendert Boer
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Teijin Aramid BV
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Teijin Aramid BV
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Assigned to TEIJIN ARAMID B. V. reassignment TEIJIN ARAMID B. V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BOER, TEUNIS LEENDERT, KOEHORST, HENDRIKUS JOHANNES
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/69—Sulfur trioxide; Sulfuric acid
    • C01B17/88—Concentration of sulfuric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F13/00—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like
    • D01F13/04—Recovery of starting material, waste material or solvents during the manufacture of artificial filaments or the like of synthetic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

Definitions

  • the invention pertains to a method of increasing the sulfuric acid concentration of a sulfuric acid solution.
  • Sulfuric acid solutions are used in various chemical processes.
  • One of these processes is the manufacture of aramid polymer.
  • the manufacture of aramid fiber is mentioned.
  • Aramid fiber is normally produced by dissolving PPTA (para-phenylene terephthalamide) or another aramid polymer in 100% sulfuric acid after which the resulting spin dope is expelled through a spinneret. Sulfuric acid is then removed from the fibers in a washing step using water, resulting in a diluted solution of approximately 10-15% sulfuric acid (H 2 SO 4 ).
  • PPTA para-phenylene terephthalamide
  • Sulfuric acid is then removed from the fibers in a washing step using water, resulting in a diluted solution of approximately 10-15% sulfuric acid (H 2 SO 4 ).
  • the diluted sulfuric acid solution can be neutralized and disregarded, resulting in a considerable emission of sulfates and the use of considerable amounts of sulfuric acid and water from an external source. Therefore, it is more convenient to recycle it. For instance, it can be concentrated to 96% sulfuric acid in a series of different distillation processes. Such process is described in WO 2009/053254.
  • a sulfuric acid recovery unit has been used wherein the sulfuric acid concentration of diluted sulfuric acid is stepwise increased to obtain 96% sulfuric acid.
  • sulfuric acid is first concentrated to 85% sulfuric acid, and then in a next step further concentrated to 96% sulfuric acid.
  • This further concentration step is performed in an apparatus with inlet and outlet comprising an evaporator vessel, pump, and heaters. These elements are connected to each other by an enameled piping system. It was now experienced that after longer periods of operating serious problems occur in the piping system.
  • the piping is enameled at its inner surface. This is necessary because sulfuric acid/water and sulfuric acid/hydrogen peroxide mixtures are extremely corrosive at elevated temperatures.
  • the only system that can be used for industrial application are pipes, usually steel pipes, with a few millimeters thick enamel coating at their inner surfaces.
  • the Forter apparatus is suitable for making concentrated sulfuric acid from diluted sulfuric acid, such as explained in the examples where 75% sulfuric acid is obtained from 41.5% sulfuric acid, and thereafter the 75% sulfuric acid is further concentrated to 98% sulfuric acid.
  • the present invention does not relate to preventing cracks in the heat exchanger but to solve the problem of occurring cracks in the evaporator vessel and pipelines, which problem does not occur when using the sulfuric acid concentrations of Forter.
  • Forter's apparatus it is not required to provide the evaporator vessel with an enamel layer (column 4, lines 3-6).
  • the invention pertains to a method of increasing the sulfuric acid concentration of a first aqueous sulfuric acid solution with a sulfuric acid concentration of 82-89% to a concentrated sulfuric acid solution with a sulfuric acid concentration of at least 90%, comprising the steps of evaporating water from the first aqueous sulfuric acid solution in an evaporator vessel to the concentrated sulfuric acid solution, pumping around a mixture of the first aqueous sulfuric acid solution, part of the concentrated sulfuric acid solution, a second aqueous sulfuric acid solution, and hydrogen peroxide through an enameled piping system comprising the evaporator vessel and one or more heaters and pumps, which piping system is operating at a temperature of at least 180° C., characterized in that the sulfuric acid concentration of the second aqueous sulfuric acid solution is at least 90%.
  • FIG. 1 is a block diagram of an evaporator process.
  • FIG. 2 is a block diagram of an evaporator process.
  • FIG. 3 is a block diagram of an evaporator process.
  • FIG. 4 is a block diagram of an evaporator process.
  • This method allows the concentration of the sulfuric acid solution up to 98% concentrated sulfuric acid. Higher concentrations of sulfuric acid up to 130% can be obtained by adding oleum or sulfur trioxide from an external source.
  • the concentrated sulfuric acid of for instance 96% as directly obtained in the process can so be further concentrated up to 130% sulfuric acid. It is common to increase the concentrated sulfuric acid in this manner to 100% or 105% sulfuric acid, for instance from 96% sulfuric acid to 100% sulfuric acid.
  • 90 to 105% more preferably 98 to 105% sulfuric acid solution is considered a suitable concentration for use in aramid fiber manufacture.
  • hydrogen peroxide or a mixture of hydrogen peroxide and a first sulfuric acid solution, or a mixture of hydrogen peroxide and a second sulfuric acid solution, or a combination of mixtures of hydrogen peroxide and a first sulfuric acid solution and hydrogen peroxide and a second sulfuric acid solution is added in order to oxidize organic contaminants and optionally sulfur dioxide if formed during the concentration process.
  • the mixtures of hydrogen peroxide and the first and/or the second sulfuric acid solution can be made as a premix.
  • a premix of hydrogen peroxide and the second sulfuric acid solution is used.
  • organic components in the acid are decomposed by oxidation with hydrogen peroxide.
  • the hydrogen peroxide is mixed with part of the 78% sulfuric acid to allow for a larger amount of hydrogen peroxide to be added, thereby increasing the conversion of organic components.
  • the second sulfuric acid solution that is used has no longer the same relatively low concentration as that of the sulfuric acid solution that is used to make the first sulfuric acid solution, but has a concentration that is at least 90%, thus higher than the concentration of the first sulfuric acid solution.
  • the second sulfuric acid solution has the same concentration as the concentrated sulfuric acid solution, so that a fraction of the concentrated sulfuric acid solution as obtained after evaporation in the evaporator vessel, optionally after addition of oleum and/or sulfur trioxide to further increase the sulfuric acid concentration, can be used for mixing with the hydrogen peroxide.
  • a 30-70% aqueous hydrogen peroxide is used, preferably aqueous 50% hydrogen peroxide solution.
  • This enables a method wherein some of the concentrated sulfuric acid solution is tapped off and mixed with the hydrogen peroxide solution.
  • feed acid the sulfuric acid solution which is used to make the first sulfuric acid solution
  • the concentrated sulfuric acid solution the hydrogen peroxide solution is preferably mixed with 96% sulfuric acid.
  • the concentrated sulfuric acid solution is further concentrated by adding oleum and/or sulfur trioxide, also fraction of this further concentrated sulfuric acid solution can be used as the second sulfuric acid solution.
  • the sulfuric acid concentration of the first aqueous sulfuric acid solution is about 85%
  • the sulfuric acid concentration of the concentrated sulfuric acid solution is 94 to 98%
  • the second aqueous sulfuric acid solution is a fraction of the concentrated sulfuric acid.
  • the first sulfuric acid solution is pumped into the enameled piping system, the water is evaporated in the evaporator vessel, the water vapor is removed and the concentrated sulfuric acid is partly pumped around and mixed with fresh first sulfuric acid solution, hydrogen peroxide and the second sulfuric acid solution, and for another part removed from the system to be further used.
  • the piping system is preferably kept at a temperature between 220 and 250° C., but the temperature may also be higher. Temperatures between 230 and 240° C. are preferred.
  • FIGS. 1 to 4 The installation for performing this method is described in FIGS. 1 to 4 .
  • FIGS. 1-4 show block diagrams of an evaporator process according to the invention.
  • the sulfuric acid is concentrated, for instance, to 96% H 2 SO 4 using an evaporator vessel.
  • the first sulfuric acid solution which for instance may be about 85% sulfuric acid as obtained by a previous concentration step, for instance from about 78% sulfuric acid to about 85% sulfuric acid, is introduced into the system after the outlet 5 of the evaporator vessel 1 and mixed with part of the concentrated sulfuric acid. Another part of the concentrated sulfuric acid is withdrawn from the system to be used, for instance, in aramid polymerization reactions and which for another part can be used to make the hydrogen peroxide/second sulfuric acid mixture.
  • the mixture of concentrated sulfuric acid solution and first sulfuric acid solution is pumped by circulation pump 3 through the piping system 4 to heaters 2 . Prior to entering the heaters 2 a pre-mix of hydrogen peroxide and second sulfuric acid solution is also entered into the system.
  • the hydrogen peroxide/second sulfuric acid mixture is preferably made as a premix of hydrogen peroxide and concentrated sulfuric acid as has been obtained from the evaporator vessel and optionally as being enriched by oleum and/or sulfur trioxide.
  • the complete mixture of concentrated, first and second sulfuric acid solution and hydrogen peroxide is concentrated in the evaporator vessel 1 by evaporation to obtain the concentrated sulfuric acid solution and the evaporated water (steam) is removed from the evaporator vessel 2 and the piping system 4 , cooled down to liquid water and reused.
  • FIGS. 2 to 4 Alternative embodiments are depicted in FIGS. 2 to 4 .
  • the process is similar to the process of FIG. 1 , but hydrogen peroxide is added as a premix with the first sulfuric acid solution ( FIG. 2 ), as premixes of both the first and the second sulfuric acid solution ( FIG. 3 ), and directly as aqueous hydrogen peroxide solution ( FIG. 4 ).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
US13/884,887 2010-11-22 2011-10-26 Method for increasing the sulfuric acid concentration of a sulfuric acid solution Active US8580224B2 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP10192021 2010-11-22
EP10192021.3 2010-11-22
EP10192021 2010-11-22
PCT/EP2011/068707 WO2012069270A1 (en) 2010-11-22 2011-10-26 Method for increasing the sulfuric acid concentration of a sulfuric acid solution

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US20130236389A1 US20130236389A1 (en) 2013-09-12
US8580224B2 true US8580224B2 (en) 2013-11-12

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US (1) US8580224B2 (ko)
EP (1) EP2643267B1 (ko)
JP (1) JP5759011B2 (ko)
KR (1) KR101910338B1 (ko)
CN (1) CN103228573A (ko)
RU (1) RU2584732C2 (ko)
WO (1) WO2012069270A1 (ko)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU209511U1 (ru) * 2021-08-17 2022-03-16 Общество с ограниченной ответственностью "Реиннольц ЛАБ" Узел перегрева олеума блока выпаривания серного ангидрида из олеума установки для выпаривания серного ангидрида из олеума
RU2771415C1 (ru) * 2021-08-17 2022-05-04 Общество с ограниченной ответственностью "Реиннольц ЛАБ" Установка для выпаривания серного ангидрида из олеума и блок выпаривания серного ангидрида из олеума этой установки

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI552950B (zh) * 2013-11-20 2016-10-11 綠美企業股份有限公司 製造硫酸的方法、設備及系統
EP3551578B1 (en) * 2016-12-12 2021-07-28 Haldor Topsøe A/S A process for increasing the concentration of sulfuric acid and equipment for use in the process
CN108726490A (zh) * 2017-04-20 2018-11-02 何庆勇 一种利用烟气余热的废硫酸提浓工艺
CN109941970A (zh) * 2019-04-24 2019-06-28 成都先进金属材料产业技术研究院有限公司 利用硫酸铝钾浓缩钛白废酸的方法
CN111068495A (zh) * 2019-12-09 2020-04-28 中国恩菲工程技术有限公司 一种含硫尾气的处理方法

Citations (4)

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Publication number Priority date Publication date Assignee Title
US2172617A (en) * 1939-09-12 Process for the production of
US3475119A (en) * 1966-12-23 1969-10-28 Richard L Hummel Production of sulphuric acid
US4274910A (en) 1979-06-13 1981-06-23 Bayer Aktiengesellschaft Evaporator for concentrating mineral acid, particularly sulphuric acid
WO2009053254A2 (en) 2007-10-23 2009-04-30 Teijin Aramid B.V. Method for spinning and washing aramid fiber and recovering sulfuric acid

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CH641126A5 (en) * 1979-06-13 1984-02-15 Bertrams Ag Process and system for regenerating sulphuric acid
US4374910A (en) * 1981-09-22 1983-02-22 General Electric Company Electrolyte for secondary electrochemical cell
US5075097A (en) * 1990-10-11 1991-12-24 Cameron Gordon M Method and apparatus for sulfuric acid concentration
DE19807632A1 (de) * 1998-02-23 1999-09-02 Bayer Ag Vorrichtung zum Konzentrieren und Reinigen von Schwefelsäure
RU2159293C1 (ru) * 2000-02-21 2000-11-20 Открытое акционерное общество "Кольская горно-металлургическая компания" Способ переработки растворов, содержащих серную кислоту и цветные металлы
CN101372320B (zh) * 2007-08-20 2011-09-07 普林克有限责任公司 用于提纯废硫酸的设备

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2172617A (en) * 1939-09-12 Process for the production of
US3475119A (en) * 1966-12-23 1969-10-28 Richard L Hummel Production of sulphuric acid
US4274910A (en) 1979-06-13 1981-06-23 Bayer Aktiengesellschaft Evaporator for concentrating mineral acid, particularly sulphuric acid
WO2009053254A2 (en) 2007-10-23 2009-04-30 Teijin Aramid B.V. Method for spinning and washing aramid fiber and recovering sulfuric acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
International Search Report dated Feb. 3, 2012 from International Application No. PCT/EP2011/068707.
Written Opinion of the International Searching Authority dated Feb. 3, 2012 from International Application No. PCT/EP2011/068707.

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU209511U1 (ru) * 2021-08-17 2022-03-16 Общество с ограниченной ответственностью "Реиннольц ЛАБ" Узел перегрева олеума блока выпаривания серного ангидрида из олеума установки для выпаривания серного ангидрида из олеума
RU2771415C1 (ru) * 2021-08-17 2022-05-04 Общество с ограниченной ответственностью "Реиннольц ЛАБ" Установка для выпаривания серного ангидрида из олеума и блок выпаривания серного ангидрида из олеума этой установки

Also Published As

Publication number Publication date
KR101910338B1 (ko) 2018-10-22
RU2013128481A (ru) 2014-12-27
RU2584732C2 (ru) 2016-05-20
EP2643267A1 (en) 2013-10-02
US20130236389A1 (en) 2013-09-12
JP5759011B2 (ja) 2015-08-05
JP2013545705A (ja) 2013-12-26
EP2643267B1 (en) 2016-09-07
KR20130116894A (ko) 2013-10-24
CN103228573A (zh) 2013-07-31
WO2012069270A1 (en) 2012-05-31

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